EP2990497A1 - Acier purifié à faible teneur en oxygène et produit en acier purifié à faible teneur en oxygène - Google Patents

Acier purifié à faible teneur en oxygène et produit en acier purifié à faible teneur en oxygène Download PDF

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EP2990497A1
EP2990497A1 EP14787606.4A EP14787606A EP2990497A1 EP 2990497 A1 EP2990497 A1 EP 2990497A1 EP 14787606 A EP14787606 A EP 14787606A EP 2990497 A1 EP2990497 A1 EP 2990497A1
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Prior art keywords
steel
rem
less
content
inclusions
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EP14787606.4A
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German (de)
English (en)
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EP2990497A4 (fr
EP2990497B1 (fr
Inventor
Michimasa AONO
Kenichiro Miyamoto
Masanobu Suzuki
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing

Definitions

  • the present invention relates to low-oxygen clean steel and a steel product produced from the low-oxygen clean steel, and particularly, to low-oxygen clean steel obtained by casting low-oxygen clean molten steel deoxidized with Al or Al-Si, and a low-oxygen clean steel product produced from the low-oxygen clean steel.
  • the Al 2 O 3 -containing inclusions particles of the Al 2 O 3 -based inclusions form clusters, or components such as CaO are incorporated, and thus the melting point of the inclusion particles is lowered. Therefore, the particles aggregate together and easily increase in size.
  • the inclusions having a size increased due to the aggregation cause deterioration in performance of a steel. Accordingly, various methods of preventing the increase in size of the inclusions have been examined. Many methods of decreasing the size of inclusions by suppressing the formation of clusters due to the aggregation of inclusion particles have been proposed.
  • Patent Documents 1 to 6 disclose a method of reducing FeO binders of alumina clusters by adding a minute amount of REM to a steel. This method is effective in reducing the FeO binders, however, the generation of coarse CaO-Al 2 O 3 -based inclusions caused by a minute amount of Ca or CaO inevitably mixed in the steel cannot be prevented only by adding REM.
  • Patent Document 7 discloses a method of reducing FeO binders of alumina clusters by adding Mg.
  • this method similarly to the method disclosed in Patent Documents 1 to 6, coarse CaO-Al 2 O 3 -MgO-based inclusions are generated by a minute amount of Ca or CaO and a minute amount of Mg or MgO which are inevitably mixed in from a refractory material for refining.
  • Patent Document 8 discloses a method of preventing the generation of coarse inclusions by further deoxidation of steel, in which "O" (dissolved oxygen) in the steel is controlled and removed with Al, in order of Ti and REM.
  • O dissolved oxygen
  • Patent Document 9 discloses a method of preventing the generation of cluster-like inclusions which cause press cracks by complex deoxidation with Al+Ti+REM.
  • deoxidation with Ti is essentially similar to the method described in Patent Document 8, and thus the method described in Patent Document 9 cannot be applied to the production of low-Ti steel.
  • the method described in Patent Document 9 cannot be applied to the production of high-cleanliness steel since it is difficult to intentionally form inclusions having 50% or greater of Al 2 O 3 under strong-deoxidation refining.
  • Patent Document 10 discloses a steel which contains SiO 2 -based stretching inclusions and in which REM is added as a deoxidizing agent to decrease T.O (total oxygen in the steel).
  • REM total oxygen in the steel
  • steel including steel for a suspension spring and a bearing Al is essentially added to provide fine crystal grains. Therefore, the base of the composition of the inclusions changes from SiO 2 to Al 2 O 3 due to the deoxidation with Al. Accordingly, the technology described in Patent Document 10 cannot be applied to AI-added steel.
  • Patent Document 11 discloses a method of improving, when REM-containing molten steel is cast, producibility upon casting by adding REM in accordance with "O" and "S" in the molten steel.
  • this method is a method for preventing the generation of REM sulfide when the REM is added, and its object is not the modification of inclusions. Accordingly, the target value of REM is significantly high.
  • Patent Document 12 discloses high-cleanliness steel having excellent fatigue properties and cold workability. However, the characteristics of Patent Document 12 relate to the adjustment of the composition of oxide-based inclusions in Si-deoxidized steel, and do not relate to the modification of Al 2 O 3 -based inclusions by the addition of REM.
  • An object of the invention is to improve mechanical characteristics by suppressing the generation of inclusions and by modifying the inclusions. Specifically, the object is to improve mechanical characteristics, particularly, fatigue properties by suppressing the generation of CaO-Al 2 O 3 -based inclusions which easily aggregate together and increase in size in Al-deoxidized steel and Al-Si-deoxidized steel containing Al 2 O 3 inclusions, by modifying the inclusions, and by controlling the form of the inclusions. In addition, an object of the invention is to provide steel in which the above-described problem has been solved, and a steel product formed of the steel. Means for Solving the Problem
  • the inventors of the invention have thought that in order to suppress the generation and coarsening of CaO-Al 2 O 3 -based inclusions which easily increase in size, it is effective to previously decrease the amount of CaO-Al 2 O 3 -based inclusions to be generated by suppressing the mixing of Ca or a Ca-containing material in molten steel, and it is also effective to modify residual CaO-Al 2 O 3 -based inclusions into inclusions having another component composition by adding some inclusion modifying materials.
  • the inventors of the invention have analyzed changes in properties of the inclusions and in characteristics of the steel by adding various substances as an inclusion modifying material. As a result, they have obtained the following knowledge.
  • the inclusions can be modified by adding, to molten steel in which T.O (total oxygen) has been sufficiently decreased by performing Al deoxidation or Al-Si deoxidation while suppressing the mixing of Ca or a Ca-containing material in the molten steel, a minute amount of REM (rare-earth elements) such as La, Ce, Pr, and Nd before the end of the deoxidation.
  • T.O total oxygen
  • REM rare-earth elements
  • T.O is a total amount of the dissolved oxygen in the steel and the undissolved oxygen contained in the inclusions etc.
  • the generation of CaO-Al 2 O 3 -based inclusions is suppressed by adding REM as described above. Furthermore, it has been found that CaO of the CaO-Al 2 O 3 -based inclusions generated in a small amount is reduced by REM, and thus the CaO-Al 2 O 3 inclusions are modified into Al 2 O 3 -based and/or REM 2 O 3 -based inclusions or composite inclusions including these inclusions.
  • the invention is based on the above-described knowledge and the gist thereof is as follows.
  • nonmetallic inclusions containing Al 2 O 3 and REM oxide which have a high melting point and hardly aggregate are dispersed in the steel.
  • the nonmetallic inclusions may contain REM sulfide, MgO, or both of REM sulfide and MgO.
  • Low-oxygen clean steel according to an embodiment of the invention (hereinafter, may be referred to as the low-oxygen clean steel according to this embodiment) will be described in detail.
  • the low-oxygen clean steel according to this embodiment contains C, Si, Mn, P, and S as fundamental elements, further contains, by mass %, 0.005% to 0.20% of Al, greater than 0% to 0.0005% of Ca, 0.00005% to 0.0004% of REM, and greater than 0% to 0.003% of T.O, and if necessary, contains other elements.
  • the REM content, the Ca content, and the T.O content satisfy the following Expressions I and 2, and preferably satisfy the following Expression 3.
  • nonmetallic inclusions which have a maximum predicted diameter of 1 ⁇ m to 30 ⁇ m measured using an extreme value statistical method under the condition in which the prediction area is 30000 mm 2 , and contain Al 2 O 3 and REM oxide are dispersed.
  • the average proportion of the Al 2 O 3 in the nonmetallic inclusions is greater than 50%.
  • the low-oxygen clean steel according to this embodiment is Al-deoxidized steel or Al-Si-deoxidized steel. 0.15 ⁇ REM / Ca ⁇ 4.00 Ca / T . O ⁇ 0.50 0.05 ⁇ REM / T . O ⁇ 0.50
  • REM is one or two or more of rare-earth elements La, Ce, Pr, and Nd.
  • nonmetallic inclusions containing fine Al 2 O 3 and REM oxide are dispersed by the "suppression of the generation of the inclusions" and the "modification of the generated inclusions".
  • the effect of the "suppression of the generation of the inclusions" is obtained by controlling the Al content, the Ca content, and the T.O content within predetermined ranges.
  • the effect of the "modification of the generated inclusions" is obtained by a minute amount of REM of 0.00005 mass % to 0.0004 mass % (to be described later in detail).
  • the inclusion modification effect of REM is obtained through a reducing action by REM with respect to CaO or CaO of CaO-Al 2 O 3 .
  • the low-oxygen clean steel it is important to control the amounts of Al, Ca, and T.O to 0.005 mass % to 0.20 mass %, to greater than 0 mass % to 0.0005 mass %, and to greater than 0 mass % to 0.003 mass %, respectively, from the viewpoint of the suppression of the generation of the inclusions, and it is important to control the amount of REM to 0.00005 mass % to 0.0004 mass % from the viewpoint of the modification of the generated inclusions.
  • steel contains C, Si, Mn, P, S, and if necessary, other elements with the remainder Fe and impurities.
  • the above-described inclusion modification effect by REM is exhibited without being affected by molten steel components such as C, Si, and Mn other than Al, Ca, REM, and T.O. That is, it is not necessary to restrict the contents of elements other than Al, Ca, REM, and T.O.
  • the inventors of the invention have confirmed this fact by way of experiment in an actual operation. The reasons for restriction of the respective contents will be described later.
  • the inventors of the invention have found that it is important for Al, Ca, REM, and T.O existing in a minute amount in the molten steel to be controlled not only in the content of each element, but also in the content ratio in order to appropriately maintain the mutual action and reaction between the elements and to maximize the inclusion modification effect by REM. Specifically, they have found that it is effective to control the ratio of REM to Ca, the ratio of REM to T.O, and the ratio of Ca to T.O as indices of the content ratios. The reasons for restriction of these content ratios will be described later.
  • % means mass %.
  • chemical components are preferably within the following ranges in specimen of steel sampled from molten steel before casting based on JIS G 0417 or specimen of steel after casting
  • A1 0.005% to 0.20%
  • Al is a deoxidizing element and is an element which makes crystal grains of steel finer.
  • the lower limit of the Al content is 0.005%.
  • the lower limit of the Al content is preferably 0.010%.
  • the molten steel When Al is contained in molten steel, the molten steel inevitably becomes Al-deoxidized molten steel and Al 2 O 3 -containing inclusions are generated in the molten steel.
  • the Al content in the molten steel is greater than 0.20%, the inclusions are generated in a large amount and remain in the steel and the fatigue properties of the steel deteriorate. Therefore, the upper limit of the Al content is 0.20%.
  • the upper limit of the Al content is preferably 0.10%.
  • Ca is a deoxidizing element and is an element which forms CaO-Al 2 O 3 -based inclusions which easily aggregate together and have a low melting point through a deoxidation reaction.
  • Al 2 O 3 -based inclusions are made into CaO-Al 2 O 3 -based composite inclusions having a low melting point and coarsen.
  • the CaO-Al 2 O 3 -based inclusions coarsening and remaining in the steel are not liquefied at a rolling temperature and remain in a coarse state in the steel.
  • the amount of Ca is preferably as small as possible, but 0.0005% or less of Ca is permissible. Accordingly, the upper limit of the Ca content is 0.0005%.
  • the upper limit of the Ca content is preferably 0.0003%, and more preferably 0.00025%.
  • the lower limit of the Ca content is greater than 0%.
  • the generation of CaO-Al 2 O 3 -based inclusions can be suppressed under the condition in which there is a minute amount of Ca incorporated inevitably in the molten steel.
  • the Ca content is adjusted before the addition of REM.
  • the method of suppressing the Ca content to 0.0005% or less in the course of refining will be described later.
  • REM is an important element which modifies CaO-Al 2 O 3 -based inclusions by reducing CaO in molten steel and CaO in inclusions.
  • the molten steel sufficiently deoxidized with Al or Al-Si contains 0.00005% to 0.0004% of REM (rare-earth element, one or two or more of La, Ce, Pr, and Nd) in order to obtain the inclusion modification effect.
  • REM rare-earth element, one or two or more of La, Ce, Pr, and Nd
  • the inclusions increase in size.
  • the detailed mechanism thereof is not clear, but is thought to be that when the molten steel contains greater than 0.0004% REM, a compound phase having a low melting point and a high REM concentration appears in the inclusions and promotes the aggregation of the inclusions, and thus the inclusions increase in size. Therefore, the upper limit of the REM content is 0.0004%.
  • the upper limit of the REM content is preferably 0.0003%, and more preferably 0.0002%.
  • the range of the REM content is based on the result of the evaluation on the relationship between steel piece extreme value statistics (maximum predicted diameter) of the nonmetallic inclusions in the low-oxygen clean steel according to this embodiment calculated through an extreme value statistical method and fatigue strength.
  • FIG. 1 is a diagram showing the relationship between a maximum diameter ( ⁇ area ( ⁇ m)) of the nonmetallic inclusions and fatigue strength (MPa). From FIG. 1 , it is found that the fatigue strength is improved with a decrease in grain diameter ( ⁇ area ( ⁇ m)) of the nonmetallic inclusions.
  • the component composition and the form (dimensions, shape) of the nonmetallic inclusions have a large influence on the fatigue strength of steel.
  • the component composition and the form (dimensions, shape) of the nonmetallic inclusions will be described later.
  • FIG. 2 shows the relationship between an REM content (ppm) and steel piece extreme value statistics ( ⁇ m).
  • the steel piece extreme value statistics ( ⁇ m) provide an estimated value (maximum predicted diameter) of the maximum diameter of the inclusions existing in a predetermined test amount (prediction area) of a steel, which is obtained through an extreme value statistical method.
  • the steel piece extreme value statistics are calculated through an extreme value statistical method with a prediction area of 30,000 mm 2 .
  • the REM content at which the steel piece extreme value statistics ( ⁇ m) are 30 ⁇ m or less is 4 ppm (0.0004%) or less.
  • T.O was 5 ppm to 20 ppm and was within a preferable range of this embodiment.
  • the upper limit of the REM content is 0.0004% based on the above description.
  • the inclusion modification effect of REM is exhibited when the REM content is 0.5 ppm or greater. Accordingly, the lower limit of the REM content is 0.00005%. That is, the REM content is 0.00005% to 0.0004%.
  • the REM content is preferably 0.00005% to 0.0003%, and more preferably 0.00005% to 0.0002%.
  • T.O greater than 0% to 0.003%
  • O is an element which exists in molten steel and forms an oxide. Accordingly, in producing steel which has excellent mechanical characteristics and in which a small amount of inclusions are finely dispersed, the T.O content is required to be controlled. In addition, it is also important to control the T.O content in the relationship with the contents of Ca and REM, which are constituent elements of oxide inclusions, in molten steel.
  • the T.O content of molten steel is greater than 0.003%, oxide inclusions are generated in a large amount and remain in the steel, and mechanical characteristics, particularly, fatigue properties of the steel deteriorate. Therefore, the T.O content is 0.003% or less.
  • the T.O content is preferably 0.002% or less, and more preferably 0.001% or less.
  • the amount of T.O is preferably as small as possible, the lower limit thereof is greater than 0% since it is difficult to adjust the amount of T.O to 0%.
  • REM is an element which reduces CaO in inclusions to act for modification of the inclusions and suppression of coarsening. Therefore, the ratio of REM to Ca which is a ratio of the REM content to Ca content is an important index for maximizing the inclusion modification effect of REM.
  • FIG. 3 shows the relationship between the ratio of REM to Ca and steel piece extreme value statistics ( ⁇ m).
  • the steel piece extreme value statistics are 30 ⁇ m or less when the ratio of REM to Ca is 0.15 to 4.00.
  • the ratio of REM to Ca is less than 0.15, the inclusions containing CaO-Al 2 O 3 as a main component are not sufficiently modified.
  • the inclusions have a grain diameter (steel piece extreme value statistics) greater than 30 ⁇ m, and thus coarsen and remain in the steel, and the mechanical characteristics thereof are not improved.
  • the steel piece extreme value statistics ( ⁇ m) are greater than 30 ⁇ m.
  • the reason for this is assumed to be that since the molten steel has an excessively high REM content, the concentration of REM oxide in the inclusions to be generated excessively increases, and thus the composition of the inclusions is out of an appropriate range.
  • the detailed mechanism thereof is not clear, but is presumed to be that when the REM concentration in the inclusions excessively increases, the inclusions aggregate together due to the generation of a low-melting-point phase in the inclusions, and as a result, the steel piece extreme value statistics ( ⁇ m) are increased.
  • the ratio of REM to Ca is 0.15 to 4.00.
  • the ratio of REM to Ca is preferably 0.20 to 3.00, and more preferably 1.00 to 3.00.
  • the ratio of Ca to T.O which is a ratio of the Ca content to the T.O content is an important index for suppressing the generation and coarsening of CaO-Al 2 O 3 -based inclusions and for maximizing the inclusion modification effect of REM.
  • FIG. 5 shows the relationship between the ratio of Cato T.O and steel piece extreme value statistics ( ⁇ m) analyzed when REM is appropriately added (steel having an REM content of 0.00005% to 0.0004%), when REM is excessively added (steel having an REM content greater than 0.0004%), and when REM is not added (the REM content is less than 0.00005%).
  • the ratio of Ca to T.O is 0.50 or less.
  • the ratio of Ca to T.O is preferably 0.10 to 0.40.
  • the ratio of Ca to T.O is preferably 0.20 or less in order to suppress the coarsening of the inclusions by Ca.
  • REM/T.O 0.05 to 0.50 (0.05 ⁇ REM/T.O ⁇ 0.50)
  • the ratio of REM to T.O is an effective index for sufficiently exhibiting the inclusion modification effect of REM. Accordingly, in addition to the ratio of REM to Ca and the ratio of Ca to T.O that have been described above, the ratio of REM to T.O is preferably 0.05 to 0.50 in order to prominently exhibit the inclusion modification effect of REM.
  • the ratio of REM to T.O is less than 0.05, there is no sufficient contribution to the reduction of CaO and CaO of CaO-Al 2 O 3 , which contribute as a binding agent of the inclusions, and thus the inclusion modification effect is not sufficiently exhibited. Therefore, the effect of finely dispersing the nonmetallic inclusions in the steel is not obtained, and thus there is no contribution to an improvement in mechanical characteristics. Accordingly, the ratio of REM to T.O is preferably 0.05 to 0.50, and more preferably 0.10 to 0.40.
  • FIG. 4 shows the relationship between the ratio of REM to T.O and steel piece extreme value statistics in steel having 0.003% or less of T.O.
  • all of the REM content, the ratio of REM to Ca, the ratio of Ca to T.O, etc. are within the ranges of the low-oxygen clean steel according to this embodiment.
  • the REM When REM satisfying the ratio of REM to T.O of 0.05 to 0.50, and preferably 0.10 to 0.40 is contained in clean molten steel having 0.003% or less of T.O, the REM sufficiently reduces CaO contributing as a binding agent in the aggregation of the inclusions and CaO of CaO-Al 2 O 3 (that is, the inclusion modification effect is sufficiently exhibited). As a result, the inclusions do not aggregate and the nonmetallic inclusions are more finely dispersed.
  • C is an effective element for securing the strength or hardness of steel after hardening.
  • Types of steels which are not required to have such strength or hardness are not essentially required to contain C. Accordingly, the lower limit of the C content is not particularly restricted.
  • C is a fundamental element of steel and it is difficult to adjust the content thereof to 0%, the content of C cannot be 0%.
  • the C content is preferably 0.001% or greater.
  • the upper limit of the C content is preferably 1.20%.
  • the upper limit of the C content is more preferably 1.00%.
  • Si is an effective element for securing the strength or hardness by improving hardenability of steel.
  • Types of steels which are not required to have such strength or hardness are not essentially required to contain Si. Accordingly, the lower limit of the Si content is not particularly restricted. However, since Si is a fundamental element of steel and it is difficult to adjust the content thereof to 0%, the content of Si cannot be0%.
  • the Si content is preferably 0.001% or greater.
  • the upper limit of the Si content is preferably 3.00%.
  • the upper limit of the Si content is more preferably 2.50%.
  • Mn is an effective element for securing the strength or hardness by improving hardenability of steel.
  • Types of steels which are not required to have such strength or hardness are not essentially required to contain Mn. Accordingly, the lower limit of the Mn content is not particularly restricted.
  • Mn is a fundamental element of steel and it is difficult to adjust the content thereof to 0%, the content of Mn cannot be0%.
  • the Mn content is preferably 0.001% or greater.
  • the upper limit of the Mn content is preferably 16.0%.
  • the upper limit of the Mn content is more preferably 12.0%.
  • the P content is an impurity element, and when the P content is too large, the toughness of steel deteriorates. Therefore, the P content is preferably restricted to 0.05% or less, and more preferably to 0.03% or less. However, large refining cost is required to decrease the P content to 0.0001% or less. Therefore, the lower limit of the P content in practical steel is approximately 0.0001%.
  • S is an impurity element, and when the S content is too large, the toughness of steel deteriorates. Therefore, the S content is preferably restricted to 0.05% or less, and more preferably to 0.03% or less. Large refining cost is required to decrease the S content to 0.0001% or less. Therefore, the lower limit of the S content in practical steel is approximately 0.0001%.
  • the low-oxygen clean steel according to this embodiment may further contain one or two or more of 3.50% or less of Cr, 0.85% or less of Mo, 4.50% or less of Ni, 0.20% or less of Nb, 0.45% or less of V, and 0.30% or less of W other than the above-described elements in such a range as not to damage the characteristics thereof. Since it is not necessary to essentially contain these elements, the lower limits thereof are 0%.
  • Cr is an effective element for securing the strength or hardness by improving hardenability of steel.
  • the Cr content is preferably 0.01% or greater to obtain this effect.
  • the upper limit of the Cr content when Cr is contained is 3.50%.
  • the upper limit of the Cr content is preferably 2.50%.
  • Mo is an effective element for securing the strength or hardness by improving hardenability of steel.
  • Mo is an element which forms carbide to contribute to an improvement in temper softening resistance.
  • the Mo content is preferably 0.001% or greater when obtaining these effects.
  • the Mo content is greater than 0.85%, a supercooling structure which causes deterioration in toughness and ductility is easily generated.
  • the upper limit of the Mo content when Mo is contained is 0.85%.
  • the upper limit of the Mo content is preferably 0.65%.
  • Ni is an effective element for securing the strength or hardness by improving hardenability.
  • the Ni content is preferably 0.005% or greater to obtain this effect.
  • the upper limit of the Ni content when Ni is contained is 4.50%.
  • the upper limit of the Ni content is preferably 3.50%.
  • Nb is an element which forms carbide, nitride, or carbonitride to contribute to the prevention of coarsening of crystal grains and an improvement in temper softening resistance.
  • the Nb content is preferably 0.001% or greater when obtaining these effects.
  • the upper limit of the Nb content when Nb is contained is 0.20%.
  • the upper limit of the Ni content is preferably 0.10%.
  • V is an element which forms carbide, nitride, or carbonitride to contribute to the prevention of coarsening of crystal grains and an improvement in temper softening resistance.
  • the V content is preferably 0.001% or greater when obtaining these effects.
  • the upper limit of the V content when V is contained is 0.45%.
  • the upper limit of the V content is preferably 0.35%.
  • W is an effective element for securing the strength or hardness by improving hardenability of steel.
  • W is an element which forms carbide to contribute to an improvement in temper softening resistance.
  • the W content is preferably 0.001% or greater when obtaining these effects.
  • the upper limit of the W content when W is contained is 0.30%.
  • the upper limit of the W content is preferably 0.20%.
  • the low-oxygen clean steel according to this embodiment may further contain, by mass %, one or two or more of 0.006% or less of B, 0.06% or less of N, 0.25% or less of Ti, 0.50% or less of Cu, 0.45% or less of Pb, 0.20% or less of Bi, 0.01% or less of Te, 0.20% or less of Sb, and 0.001% or less of Mg other than the above-described elements in such a range as not to damage the characteristics thereof. Since it is not necessary to essentially contain these elements, the lower limits thereof are 0%.
  • B is an element which increases hardenability of steel to contribute to an improvement in strength.
  • B is an element which is segregated in austenite grain boundaries to suppress the grain boundary segregation of P and to improve fatigue strength.
  • the B content is preferably 0.0001% or greater when obtaining these effects. When the B content is greater than 0.006%, the effect is saturated and embrittlement is caused. Therefore, the upper limit of the B content is 0.006% when B is contained.
  • the upper limit of the B content is preferably 0.004%.
  • N is an element which forms fine nitride to provide fine crystal grains and contributes to an improvement in strength and toughness.
  • the N content is preferably 0.001% or greater when obtaining these effects.
  • the upper limit of the N content is 0.06% when N is contained.
  • the upper limit of the N content is preferably 0.04%.
  • Ti is an element which forms fine Ti nitride to provide fine crystal grains and contributes to an improvement in strength and toughness.
  • the Ti content is preferably 0.0001 % or greater when obtaining these effects.
  • the upper limit of the Ti content is 0.25% when Ti is contained.
  • the upper limit of the Ti content is preferably 0.15%.
  • Cu is an element which increases corrosion resistance of steel.
  • the Cu content is preferably 0.01% or greater to obtain this effect.
  • the upper limit of the Cu content is 0.50% when Cu is contained.
  • the upper limit of the Cu content is preferably 0.30%.
  • Pb is an element which contributes to an improvement in machinability of steel.
  • the Pb content is preferably 0.001% or greater to obtain this effect.
  • the upper limit of the Pb content is 0.45% when Pb is contained.
  • the upper limit of the Pb content is preferably 0.30%.
  • Bi is an element which contributes to an improvement in machinability of steel.
  • the Bi content is preferably 0.001% or greater to obtain this effect.
  • the upper limit of the Bi content is 0.20% when Bi is contained.
  • the upper limit of the Bi content is preferably 0.10%.
  • Te is an element which contributes to an improvement in machinability of steel.
  • the Te content is preferably 0.0001% or greater to obtain this effect.
  • the upper limit of the Te content is 0.01% when Te is contained.
  • the upper limit of the Te content is preferably 0.005%.
  • Sb is an element which contributes to an improvement in corrosion resistance based on sulfuric acid resistance and hydrochloric acid resistance and an improvement in machinability.
  • the Sb content is preferably 0.001% or greater when obtaining these effects.
  • the upper limit of the Sb content is 0.20% when Sb is contained.
  • the upper limit of the Sb content is preferably 0.10%.
  • Mg is an element which contributes to an improvement in machinability of steel.
  • the Mg content is preferably 0.0001 % or greater to obtain this effect.
  • the upper limit of the Mg content is 0.01% when Mg is contained.
  • the upper limit of the Mg content is preferably 0.005%.
  • the low-oxygen clean steel according to this embodiment is obtained by adding, by mass %, 0.00005% to 0.0004% of REM to molten steel which contains 0.005% to 0.20% of Al, 0.0005% or less of Ca, and 0.003% or less of T.O and in which the ratio of Ca to T.O is 0.50 or less.
  • the low-oxygen clean steel according to this embodiment satisfies (x1) the ratio of REM to Ca is 0.15 to 4.00 and (y) the ratio of Ca to T.O is 0.50 or less, and preferably further satisfies (x2) the ratio of REM to T.O is 0.05 to 0.50.
  • Molten steel having the following chemical components: 0.005% to 0.20% of Al; 0.0005% or less of Ca; and 0.003% or less of T.O, in which the ratio of Ca to T.O is 0.50 or less, is used when obtaining the low-oxygen clean steel according to this embodiment.
  • the amount of CaO existing in the molten steel and the amount of CaO-Al 2 O 3 inclusions are small.
  • the REM When REM is added to the molten steel in the above state in an amount of 0.00005% to 0.0004% such that the above-described (x1) (preferably further (x2)) is satisfied, the REM reduces CaO, acting as a binding agent to promote the aggregation of the inclusions, FeO, compounds such as FeO-Al 2 O 3 , and CaO in CaO-Al 2 O 3 inclusions.
  • the CaO-Al 2 O 3 inclusions are modified into Al 2 O 3 -based and/or REM 2 O 3 -based inclusions, and (ii) the aggregation of Al 2 O 3 -based inclusions, Al 2 O 3 -MgO-based inclusions, and REM 2 O 3 -based inclusions is suppressed, whereby the inclusions do not coarsen.
  • the low-oxygen clean steel according to this embodiment obtained by casting the molten steel in which the fine nonmetallic inclusions exist is capable of obtaining a structure in which the nonmetallic inclusions are finely dispersed.
  • the nonmetallic inclusions are fine and have a size of 30 ⁇ m or less even in terms of the maximum predicted diameter obtained using an extreme value statistical method with a prediction area of 30,000 mm 2 .
  • the nonmetallic inclusions are fine, fatigue fracture hardly occurs therefrom as is apparent fracture-mechanically. Therefore, the mechanical characteristics, particularly, fatigue properties of the low-oxygen clean steel according to this embodiment are significantly improved. This is the most important characteristic of the low-oxygen clean steel according to this embodiment.
  • the maximum predicted diameter of the inclusions is a value estimated using, for example, the extreme value statistical method described in " Metal Fatigue, Effects of Micro-Defects and Inclusion” (written by Yukitaka Murakami, Yokendo, published in 1993, P.223 to 239 ).
  • FIG. 6 shows typical forms of nonmetallic inclusions existing in steel (SEM reflected electron image). These are forms of nonmetallic inclusions detected when evaluating steel piece extreme value statistics in examples to be described later.
  • FIGS. 6(a) and 6(b) show forms of nomnetallic inclusions of invention examples (No. 2-1 in Tables 2-1 and 2-2 to be shown later) (type of steel: suspension spring A), and
  • FIGS. 6(c) and 6(d) show representative forms of nonmetallic inclusions of comparative examples (No. 2-2 in Tables 2-1 and 2-2 to be shown later) (type of steel: suspension spring A).
  • the diameter (see black borders) of the nonmetallic inclusions of the comparative examples shown in FIGS. 6(c) and 6(d) is on the order of tens of- ⁇ m.
  • the diameter (see black borders) of the nonmetallic inclusions of the invention examples shown in FIGS. 6(a) and 6(b) is on the order of several- ⁇ m.
  • "Fine nonmetallic inclusions" exist in various shapes in the low-oxygen clean steel according to this embodiment as shown in FIGS. 6(a) and 6(b) . Since the nonmetallic inclusions are fine due to the modification with REM, fatigue fracture hardly occurs therefrom. The inventors of the invention have confirmed this fact by way of experiment in an actual operation with respect to main types of steels which are used in spring steel, bearing steel, case hardening steel etc.
  • Table 1 shows component compositions of the above-described nonmetallic inclusions shown in FIGS. 6(a) to 6(d) .
  • Table 1 also shows component compositions, which are separately observed from those in FIGS. 6(a) to 6(d) , of nonmetallic inclusions (Invention Examples 3 to 12) of the low-oxygen clean steels according to this embodiment and nonmetallic inclusions (Comparative Examples 3 to 6) of comparative steels.
  • the component composition of the nonmetallic inclusions was measured as follows.
  • the average composition of one inclusion detected by an optical microscope is measured using an energy dispersive X-ray analysis method to analyze the composition of Mg, Al, Si, Ca, La, Ce, Nd, Mn, Ti, and S. Since Mn and Ca form both of oxide and sulfide, S is allowed to form sulfide in order of MnS and CaS and the remaining Ca and Mn are analyzed as oxide.
  • the number average may be taken after examining the compositions of a plurality of inclusions as described above.
  • the nonmetallic inclusions shown in FIG. 6 have a difference in contrast therebetween. This shows that the nonmetallic inclusions have a mixed phase of oxide and sulfide, but the fact that the nonmetallic inclusions have a mixed phase does not have a dominant influence on fatigue properties. This is consistent with the relationship between the grain diameter of the nonmetallic inclusions and the fatigue strength shown in FIG. 1 .
  • FIGS. 6(a) and 6(b) are shown in Invention Examples 1 and 2 of Table 1, and the inclusion compositions of FIGS. 6(c) and 6(d) are shown by mass % in Comparative Examples 1 and 2 of Table 1.
  • Comparative Examples 1 and 2 and further Comparative Examples 3 to 6 the inclusions are not modified with REM.
  • Invention Examples 1 and 2 and further Invention Examples 3 to 12 the inclusions are modified with REM.
  • Al 2 O 3 and/or CaO are main components in Comparative Examples I and 2 and further Comparative Examples 3 to 6.
  • Al 2 O 3 and REM oxide are main components in Invention Examples 1 and 2 and further Invention Examples 3 to 12.
  • the average proportion of Al 2 O 3 in the inclusions in each example exceeds 50%.
  • CaO in Comparative Examples 1 is 16.5% and CaO in Comparative Example 2 is 24.3%. These are values higher than 10%.
  • CaO is 1.0% or less and significantly lower than in the comparative examples.
  • TiO 2 and SiO 2 are almost undetected (for example, 1.0% or less).
  • the nonmetallic inclusions almost contain no TiO 2 and SiO 2 .
  • a preferable low-oxygen clean steel according to this embodiment will be described.
  • a low-oxygen clean steel according to an embodiment is preferably obtained by rolling a steel piece obtained through a refining process and a casting process or the like.
  • processing processes such as the casting process and rolling, arbitrary methods can be employed so as to provide a desired shape and desired characteristics.
  • the low-oxygen clean steel it is important to add, by mass %, 0.00005% to 0.0004% of REM to molten steel which contains 0.005% to 0.20% ofAl, 0.0005% or less of Ca, and 0.003% or less of T.O and in which the ratio of Ca to T.O is 0.50 or less.
  • the Ca content is preferably restricted and REM is preferably contained in the molten steel through the following method in the following manner.
  • auxiliary raw materials and alloy iron are added to molten steel when the molten steel is subjected to refining and component adjustment.
  • the auxiliary raw materials and alloy iron contain Ca in various forms, it is important to manage the timing of addition of the auxiliary raw materials and alloy iron and the Ca content contained therein in order to adjust the Ca content to 0.0005% or less.
  • Ca in the alloy iron is contained as an alloy component at a high ratio. Accordingly, in the case of molten steel deoxidized with A1 or Al-Si, the yield of Ca in the molten steel is high. Thus, it is necessary to avoid the addition of alloy iron having a high Ca content.
  • the amount of Ca to be added is preferably decreased using, for example, alloy iron having 1.0% or less of Ca.
  • quicklime, dolomite etc. to be added as a slag-making material contain Ca in the form of mainly oxide, it is incorporated in slag when floating separation is sufficiently conducted. However, since the floating separation cannot be sufficiently conducted during the terminal stages of secondary refining, the addition is avoided.
  • Other than quicklime, dolomite, CaO-containing recycle slag may be used as a slag-making material.
  • CaO adheres to inclusions having Al 2 O 3 as a main component and functions as a binding agent to promote coarsening.
  • REM acting to reduce the CaO is added in an amount of 0.00005% to 0.0004% to molten steel in which ladle slag refining has been completed by sufficient deoxidation with Al or Al-Si. It is not preferable that REM be added before deoxidation with Al or Al-Si be performed since the inclusions coarsen.
  • molten steel is deoxidized by ladle electrode heating, and then REM is added to the molten steel in the vacuum degassing process.
  • REM may be added to a tundish or the molten steel in a mold.
  • the molten steel is preferably stirred to uniformize the REM concentration in the molten steel after the addition.
  • stirring in a vacuum chamber in the vacuum degassing process stirring in the tundish by flowing of the molten steel, and electromagnetic stirring in the mold can be applied.
  • REM may be added in the form of any of pure metal such as Ce and La, alloy of REM metals, or alloy with other alloys.
  • the shape thereof is preferably a lump-like shape, a grain shape, or a wire shape from the viewpoint of yield.
  • a low-oxygen clean steel product according to this embodiment can be produced by processing the low-oxygen clean steel according to this embodiment using an arbitrary method.
  • a steel piece was produced by casting molten steel having a component composition shown in Table 2-1.
  • the slag composition and the conditions of auxiliary raw materials at the time of refining are shown together in Table 2-2.
  • a Ca source CaSi or FeSi
  • the component composition includes the remainder Fe and impurities.
  • FIGS. 6(a) and 6(b) show the forms of the nonmetallic inclusions of Invention Example No. 2-1, and FIGS. 6(c) and 6(d) show the forms of the nonmetallic inclusions of Comparative Example 2-2.
  • the steel piece extreme value statistics of No. 1-1 are 18.8 ⁇ m ( ⁇ 30 ⁇ m).
  • the inclusions were not modified and the steel piece extreme value statistics were 31.0 ⁇ m.
  • fatigue fracture occurs from the inclusions.
  • the steel piece extreme value statistics of the inclusions in the table were calculated using an extreme value statistical method in the following manner.
  • the invention steel was cast by a curved continuous casting machine, and then in a steel piece rolled at a surface reduction ratio of 1.8 or greater, a steel sample was collected from a portion at a position of 1/4 from the loose surface side of an L-cross-section of the steel piece (a cross-section including a center line of a loose surface, a center line of a surface opposite thereto, and a center line of the steel piece) and the steel piece extreme value statistics were calculated based on an extreme value statistical method including measurement under the conditions of an test standard area of 100 mm 2 (area of 10 mm ⁇ 10 mm), a test field of 16 (that is, the number of tests is 16), and an area for performing prediction of 30,000 mm 2 .
  • ⁇ area (max) (a 2 +b 2 ) 1/2 where a is a major axis and b is a minor axis perpendicular to the major axis.
  • the loose surface is a surface on the upper surface side in a horizontal portion from a curved portion of the curved continuous casting machine.
  • the estimation of the maximum predicted diameter ( ⁇ area (max)) of the inclusions using extreme value statistics is performed according to the method described in, for example, "Metal Fatigue, Effects of Micro-Defects and Inclusions" (written by Yukitaka Murakami, Yokendo, published in 1993, P.223 to 239 ).
  • the used method is a two-dimensional method of estimating maximum inclusions observed in a certain area by two-dimensional examination.
  • the maximum predicted diameter ⁇ area (max) of the inclusions in the prediction area (30,000 mm 2 ) was estimated from the test standard area (100 mm 2 ) from the image of the nonmetallic inclusions imaged by an optical microscope. Specifically, 16 pieces of data (data of 16 fields) on maximum diameters of the inclusions obtained through the observation were plotted on extreme value probability paper in accordance with the method described in the document to obtain a maximum inclusion distribution straight line (linear function of the maximum inclusion and the extreme value statistical standardization variable), and the maximum inclusion distribution straight line was extrapolated to estimate a maximum predicted diameter ⁇ area (max) of the inclusions in the area of 30,000 mm 2 .
  • FIG. 7 shows an aspect of the production of the radial rolling fatigue test piece.
  • FIG. 7(a) shows the shape of the material of the radial rolling fatigue test piece
  • FIG. 7(b) shows an aspect of the collection of the radial rolling fatigue test piece
  • FIG. 7(c) shows a final shape of the collected radial rolling fatigue test piece.
  • test piece From the material of the radial rolling fatigue test piece (hereinafter, referred to as "test piece") of ⁇ 65 mm, a round bar (having a center hole at both ends and a through hole of ⁇ 3 mm in one end portion at a position separate from the end surface by 5 mm) having the shape ( ⁇ : 12.2 mm, length: 150 mm) shown in FIG. 7(a) was produced.
  • This round bar was heated for 30 minutes at 840°C in an induction heating furnace, and then subjected to quench with oil at 50°C. Thereafter, it was annealed for 90 minutes at 180°C and air-cooled. From the round bar after the heat treatment, both ends of the round bar were discarded as shown in FIG. 7(b) , and four 22 mm-test pieces having the final shape shown in FIG. 7(c) were collected from a center portion thereof and provided to the radial rolling fatigue test.
  • the radial rolling fatigue test was performed on 12 test pieces under the conditions of a test load of 600 kgf, a repetition rate of 46240 cpm, and the number of times of stopping of 1 ⁇ 10 8 using a radial rolling fatigue test machine (product name: "cylindrical fatigue life test machine” manufactured by NTN Corporation).
  • FIG. 8 shows the relationship between the maximum predicted diameter (steel piece extreme value statistics) of each test piece, obtained through the extreme value statistical method, and the shortest breaking life obtained through the radial rolling fatigue test. 8 ⁇ 10 7 or greater of the shortest breaking life is obtained when the steel piece extreme value statistics are 30 ⁇ m or less.
  • FIG. 9 shows a shape of a test piece produced for evaluation of the rotary bending fatigue properties.
  • the Ono-type rotary bending test was performed.
  • the test piece was subjected to induction hardening (frequency: 100 kHz). Tap water or a polymer quenching catalyzer was used as a refrigerant in the induction hardening. After hardening, a tempering treatment was performed for 1 hr at 150°C. Table 3 shows the test results, and F1G. 10 shows the relationship between maximum stress and the number of times of endurance.
  • the invention steel has much better fatigue properties than the conventional steel. Therefore, it is apparent that the life of a steel product produced from the invention steel increases significantly.
  • high-melting-point Al 2 O 3 -REM oxide which has CaO-Al 2 O 3 -based inclusions modified by adding a minute amount of REM to Al-deoxidized molten steel or Al-Si-deoxidized molten steel and hardly aggregates, and fine nonmetallic inclusions containing REM sulfide, MgO, or both of REM sulfide and MgO exist in the steel. Accordingly, steel having excellent fatigue properties can be provided and an improvement in other mechanical characteristics can also be expected. As a result, since the life of a steel product produced from the steel of the invention increases significantly, the invention is highly applicable in steel production industries and in steel working industries.

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JP4762725B2 (ja) 2006-01-12 2011-08-31 新日本製鐵株式会社 薄鋼板用連続鋳造鋳片とその製造方法および薄鋼板とその製造方法圧延方法
CN101675177A (zh) * 2007-03-05 2010-03-17 住友金属工业株式会社 冷轧钢板和合金化熔融镀锌钢板以及它们的制造方法
JP4485561B2 (ja) 2007-10-02 2010-06-23 株式会社神戸製鋼所 母材靭性に優れた溶接用高張力厚鋼板
CN101845590A (zh) 2009-03-25 2010-09-29 株式会社神户制钢所 焊接热影响部的韧性优良的钢材
JP5541002B2 (ja) * 2010-08-26 2014-07-09 新日鐵住金株式会社 耐水素誘起割れ性に優れた鋼材
JP5158271B2 (ja) 2011-02-24 2013-03-06 新日鐵住金株式会社 伸びフランジ性と曲げ加工性に優れた高強度鋼板およびその溶鋼の溶製方法
WO2012115181A1 (fr) * 2011-02-24 2012-08-30 新日本製鐵株式会社 Feuille d'acier à haute résistance présentant une déformabilité de bordage par étirage supérieure et une aptitude supérieure à la flexion, et procédé de préparation d'acier de lingot

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CN110205443A (zh) * 2019-06-21 2019-09-06 中天钢铁集团有限公司 一种低碳含硅铝镇静钢超低氧冶炼方法
CN110205443B (zh) * 2019-06-21 2021-05-04 中天钢铁集团有限公司 一种低碳含硅铝镇静钢超低氧冶炼方法
WO2021046938A1 (fr) * 2019-09-10 2021-03-18 中国科学院金属研究所 Acier de terres rares ultra propre et procédé de commande de modification de substances étrangères occluses

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EP2990497A4 (fr) 2016-11-30
CA2909232C (fr) 2017-04-25
CA2909232A1 (fr) 2014-10-30
JPWO2014175377A1 (ja) 2017-02-23
BR112015026523B1 (pt) 2020-02-11
US10526686B2 (en) 2020-01-07
WO2014175377A1 (fr) 2014-10-30
PL2990497T3 (pl) 2018-11-30
EP2990497B1 (fr) 2018-06-06
BR112015026523A2 (pt) 2017-07-25
KR20150131392A (ko) 2015-11-24
KR101719946B1 (ko) 2017-03-24
CN105164294B (zh) 2017-08-04
JP5935944B2 (ja) 2016-06-15
ES2674870T3 (es) 2018-07-04
CN105164294A (zh) 2015-12-16
US20160053352A1 (en) 2016-02-25

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